Ring-Opening in the Actinide Cyclopropyl Complexes [Cp3U(2,2-Diphenylcyclopropyl)] n- (n=0, 1)

被引：1

作者：

Ordonez, Osvaldo ^{[1
]}

Kent, Greggory T. ^{[1
]}

Schuerlein, Megan A. ^{[1
]}

Wu, Guang ^{[1
]}

Hayton, Trevor W. ^{[1
]}

机构：

[1] Univ Calif Santa Barbara, Dept Chem & Biochem, Santa Barbara, CA 93106 USA

来源：

ORGANOMETALLICS | 2023年 / 42卷 / 17期

关键词：

C-H ACTIVATION; BOND-CLEAVAGE; REACTIVITY; CARBENE; LIGAND; CHEMISTRY; MECHANISMS; OXIDATION; INSERTION;

D O I：

10.1021/acs.organomet.3c00222

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The reaction of [Cp3UCl] with in situ generated 1-lithium-2,2-dipenylcyclopropane results in the formationof [Cp3U(2,2-diphenylcyclopropyl)] (1) ingood yield. Reduction of 1 with KC8, in thepresence of 2.2.2-cryptand, results in the formation of a rare U(III)alkyl complex, [K(2.2.2-cryptand)][Cp3U(2,2-diphenylcyclopropyl)](2). Thermolysis or photolysis of 1 for10 d in toluene results in isomerization to the U(IV) & eta;(1)-allyl complex, [Cp3U(& eta;(1)-3,3-diphenylallyl)](3). Moreover, photolysis of 2 in THF for9 h at room temperature results in isomerization to the U(III) & eta;(1)-allyl complex, [K(2,2,2-cryptand)][Cp3U(& eta;(1)-3,3-diphenylallyl)] (4). Both 3 and 4 were fully characterized. In addition, selectivelabeling of the C-& alpha; positions of 1 and 2 with deuterium revealed that cyclopropyl ring-opening occursvia distal C-C bond cleavage via a hypothesized & eta;(3)-allyl intermediate.

引用

页码：2347 / 2352

页数：6

共 46 条

[31] Three coordinated first row-transition metal complexes, [M{N (SiMe 3 ) 2 } 3 ]-1/0: Structure, bonding, and magnetic properties [J].

Patra, Shanti Gopal ;

Chattaraj, Pratim Kumar .

POLYHEDRON, 2024, 256

[32] Structures and Vibrational Frequencies of Gas Phase and Solvated Uranyl Complexes UO2Ln2-n*a(L=F-, CO32-, NO3-; n=0-6, a=1, 2) [J].

Gu Jia-Fang ;

Lu Chun-Hai ;

Chen Wen-Kai ;

Xu Ying ;

Meng Jin-De .

ACTA PHYSICO-CHIMICA SINICA, 2009, 25 (04) :655-660

[33] Bis[N-(2,6-di-t-butyl-1-hydroxyphenyl)salicylideneaminato]palladium(II) complexes and their radical intermediates generated by PbO2 and PPh3 [J].

Veli T. Kasumov ;

Bünyamin Karabulut ;

Ibrahim Kartal ;

Fevzi Köksal .

Transition Metal Chemistry, 2001, 26 :64-70

[34] Spectroscopic, DFT and antimicrobial activity of Zn(II), Zr(IV), Ce(IV) and U(VI) complexes of N,N- chelated 4,6-bis (4-chlorophenyl)-2-amino-1,2-dihydropyridine-3-carbinitrile [J].

Sadeek, S. A. ;

Abd El-Hamid, S. M. ;

Zordok, W. A. .

APPLIED ORGANOMETALLIC CHEMISTRY, 2018, 32 (09)

[35] Theoretical Study of the Structural, Optoelectronic, and Reactivity Properties of N-[5′-Methyl-3′-Isoxasolyl]-N-[(E)-1-(-2-)]Methylidene] Amine and Some of Its Fe2+, Co2+, Ni2+, Cu2+, and Zn2+ Complexes for OLED and OFET Applications [J].

Tendongmo, Hilaire ;

Tasheh, Stanley Numbonui ;

Tamafo, Didier Aymard Fouegue ;

Bine, Fritzgerald Kogge ;

Numbonui Ghogomu, Julius .

JOURNAL OF CHEMISTRY, 2022, 2022

[36] Synthetic and Mechanistic Pathways of Cis and Trans-Hydroxytamoxifen Drug Derivatives Reacting with Cp*Rh Complexes that involve η1-N, η2-N,O, η1-O, and η6 Bonding Modes, via a Novel N-π Rearrangement; Relative Binding Affinities and Computer Docking Studies of Cis and Trans-η6-Cp*Rh-Hydroxytamoxifen Complexes at the Estrogen, ERα and ERβ Receptors, and Growth Inhibition to Breast Cancer Cells [J].

Top, Siden ;

Efremenko, Irene ;

Rager, Marie Noelle ;

Vessieres, Anne ;

Yaswen, Paul ;

Jaouen, Gerard ;

Fish, Richard H. .

INORGANIC CHEMISTRY, 2011, 50 (01) :271-284

[37] Synthesis, characterization, electrochemical properties and antibacterial activity of some transition metal complexes with 2-[N-(2′-hydroxy-1′-naphthylidene)amino]-3-carboxyethyl-4,5-dimethylthiophene [J].

Daniel, Varughese P. ;

Pillai, T. Prasanna Chandran ;

Kumari, B. Sindhu ;

Joseyphus, R. Selwin ;

Mohanan, K. .

JOURNAL OF THE INDIAN CHEMICAL SOCIETY, 2011, 88 (11) :1639-1646

[38] Neodymium monochloride and monoallyl complexes {2-[Ph2P(O)]C6H4NC(But)N(2,6-Me2C6H3)}2NdR (R = Cl, CH2CH=CH2) with the tridentate amidinate ligand in the catalysis of ring-opening polymerization of cyclic esters [J].

Tolpygin, A. O. ;

Linnikova, O. A. ;

Kovylina, T. A. ;

Cherkasov, A. V. ;

Fukin, G. K. ;

Trifonov, A. A. .

RUSSIAN CHEMICAL BULLETIN, 2020, 69 (06) :1114-1121

[39] Thermal C-H Bond Activation of Benzene with Cationic [Pt(CX3(L)]+ Complexes in the Gas Phase: A Combined Experimental/Theoretical Study (X = H, D; L=1,10-Phenanthroline, 2,2′-Bipyrimidine, 2,2′-Bipyridine, and (o,o′-Cl2C6H3)N=C(CH3)-C(CH3)=N(o,o′-Cl2C6H3)) [J].

Butschke, Burkhard ;

Schroeder, Detlef ;

Schwarz, Helmut .

ORGANOMETALLICS, 2009, 28 (15) :4340-4349

[40] Synthesis and pharmacological activity of N-(2,2-dimethyl-3,4-dihydro-2H-1-benzopyran-4-yl)-4H-1,2,4-benzothiadiazine-3-carboxamides 1,1-dioxides on rat uterus, rat aorta and rat pancreatic β-cells [J].

Khelili, Smail ;

Kihal, Nadjib ;

Yekhlef, Mohamed ;

de Tullio, Pascal ;

Lebrun, Philippe ;

Pirotte, Bernard .

EUROPEAN JOURNAL OF MEDICINAL CHEMISTRY, 2012, 54 :873-878

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